Process for preparing sodium borate compositions



United States Patent M 3,531,278 PROCESS FOR PREPARING SODIUM BORATE COMPOSITIONS Nelson P. Nies, Laguna Beach, Calif., assignor to United States Borax & Chemical Corporation, Los Angeles, Calif., a corporation of Nevada No Drawing. Filed Mar. 20, 1967, Ser. No. 624,206 Int. Cl. A01n 11/00 U.S. Cl. 71128 11 Claims ABSTRACT OF THE DISCLOSURE Noncaking and dust free sodium borate compositions having a mole ratio of Na O/B O of less than 0.5 are prepared in the form of particles containing sodium pentaborate by adding 3 to 12 percent water to a tumbling mixture of particles of either boric acid, boric oxide, metaboric acid or sodium pentaborate with anhydrous borax, borax pentahydrate, borax decahydrate or sodium pentaborate and heating the moist tumbling mixture to a temperature of 70-115" C.

BACKGROUND OF THE INVENTION Sodium borate compositions are extensively utilized as concentrated solutions applied to wood products as a fire retardant or applied to foliage to kill Weeds or defoliate plants and the like. The utilization and stabilization of such concentrated solutions is disclosed in Pats. Nos. 2,643,947 and 2,662,810.

It is much more practical and economical to handle, ship and store sodium borate compositions in dry form readily reconstitutable to a solution of desired concentration. Consumers prefer that the bulk packaged product be substantially dust free and noncaking during storage and should quickly and completely dissolve in Water to form a solution of known concentration at the time it is to be utilized.

DESCRIPTION OF THE PRIOR ART Sodium borate compositions having mole ratios of Na O/B O less than 0.5 can be made by mixing borax or boric acid with crystalline sodium pentaborate or by mixing borax or boric acid with at least one of the compounds in anhydrous form. However, the expense of the previous manufacture in the crystallization of sodium penataborate or the dehydration of borax or boric acid renders these processes undesirable. Furthermore, the mixtures including anhydrous materials dissolve in water slowly.

Untreated mixtures of boric acid and borax pentahydrate severely cake during storage. Drying these products in a double drum dryer reduces caking tendency but again is uneconomical because of the cost of steam and handling and in some cases the product can be flaked only with very slow rotation of the drums. The above compositions which are mechanical mixtures of dilferent compounds are subject to segregation of the components so that homogeneity cannot be assured on withdrawing a set portion for solution in water.

3,531,278 Patented Sept. 29, 1970 Pat. No. 2,998,310 discloses an homogenous, soluble sodium borate composition, not subject to segregation, prepared by spray drying a water solution of soluble compounds such as boric acid, sodium pentaborate, sodium tetraborate and sodium metaborate mixed in a ratio to yield the desired final Na O/B O ratio. The final product is a very finely divided, partially hydrated sodium borate, typically less than about 200 mesh with an appreciable portion of the particles less than 350 mesh.

The spray drying process requires several steps with associated equipment. The concentrated feed solution must be heated to dissolve the compounds such as in a steam heated tank, the air is preheated and the solution and air are then delivered to a spray drying chamber and the warm solution atomized into the hot air. The warm particles are cooled and separated. The expense of equipment, the energy to heat the air and the feed solution and the time and personnel involved in carrying out the several procedures, as Well as the ultrafine product obtained must be balanced against advantages in the noncaking, nonsegregating, quickly dissolving product that is obtained.

BRIEF DESCRIPTION OF THE INVENTION It has now been discovered that readily soluble, partially hydrated sodium borate compositions having a Na O/B O molar ratio of less than 0.50 and preferably between 0.1 to 0.35 can be readily and conveniently prepared in a homogenous, solid form involving no fine dust in a much simpler and less costly operation. The process involves the use of simple equipment, moderate temperatures and can utilize the least expensive starting materials. The product retains the advantages of the spray-dried product with the additional advantage of the absence of fines. The product has reduced caking tendency, dissolves readily in water, and is in a medium density form very suitable for bulk packaging. The particles, even though they contain appreciable water of hydration, have little tendency to cake and are free-flowing since they do not contain the sharp, fine edge surfaces typically associated with crystalline materials. The component ingredients are intimately dispersed throughout each particle, but yet are stationary within each particle, and thus equal portions of the material will have a uniform composition and will form a solution of level concentration.

The compositions are produced in accordance with the invention by addition of 3 to 12 percent water to an agitated mixture of sodium borate forming materials such as particles of borax and boric oxide or various equivalents for these compounds such as metaboric acid or sodium pentaborate in the desired final Na O/B O ratio and then heating the mixture to C. to C. The borax may be anhydrous or in a pentahydrated or decahydrated form. The boric acid may be in an anhydrous (boric oxide) form or may be added as metaboric acid. Sodium pentaborate may be mixed with any of the above compounds to form compositions having an Na O/B O mole ratio of not more than 0.5.

During agitation of the moist mixture, the finer particles and the surface layer of the larger particles of the borax and boric acid are dissolved, forming sodium pentaborate 3 and agitation is continued with the particles in light rolling contact for a time interval sufficient for this sodium pentaborate phase to become associated With the remaining undissolved granules. The solution of the surface of the larger particles is believed to smooth the sharp edges A more thorough understanding of the invention, its advantages and manner of operation and performance can be had from the following description of a typical preferred manner in which it can be carried out, it being understood that many changes may be made in the of these surfaces, a factor which otherwise contributes 5 specific detail of the described procedure and that equivato caking. The dissolution of the smaller particles obviouslent methods and materials may be used Without departly lliminates fines.d d f h l b ing from the scope of the invention.

e intensity an uration o agitation s ou d e controlled especially during drying to avoid reformation of S S 5 lines by attrition. Generally, the mixing rate is mild and tumbling at below about 60 rpm, is sufiicient. Less than Laboratory scale experiments are conducted by placing two hours of mixing generally is satisfactory and d a mixture of borax or boric acid granules or the various tageously the product can be prepared in less than one q iv l n in a h ll of a laboratory r y x r pr hour of mixing, 15, vided with two lifters mounted at a slanting angle. On

The manner of adding the ater can also influence the rotation Of the shell at 46 r.p.In., the granules are lifted size distribution of the product. Stirring the particles durand mixed with a tumbling action. A predetermined ing water addition minimizes local agglomeration and quantity of Water is added gradually to the tumbling mixaddition of the water as a coarse or fine spray rather than ture as a coarse or fine stream from a wash bottle. Tumlocally or instantaneously further avoids balling and 2 bling of the mixture is continued at ambient temperature lumping of the particles, and adherence of the mixture C. to 40 C.) until the water is absorbed, the mixto the walls of the mixing chamber. ture appearing to be dry.

The water and the mixture are preferably at a moderate The mixture is then partially dried by contacting the temperature below 40 C. to avoid formation of a sticky, exterior of the shell with hot air and then with a gas viscous mass. Addition of ambient temperature water to flame until a desired temperature is attained. Mixing is an unheated mixture results in a slight rise in tempera- Continued until the product is cool. Lumps, if present, ture not requiring external cooling. Amounts of water are removed with a 12 or 16 mesh screen and can be above about 12 percent may turn the mixture into a viscrushed and added to the product. cous mass and amounts below about 3 percent are in- In a first series of experiments the effect of water on adequate to sufiiciently eliminate fines and caking tendthe presence of fines and the qualitative makeup of the ency. It has been found that optimum results are obgranules is demonstrated. The starting material consists tained with control of water between 5 to 10 percent. In of a mixture of 300 grams of borax 5 mol, technical grade the absence of water, no sodium pentaborate is formed (T.G.)(l5% through 100 mesh) and 700 grams of fine and the mixture is more dusty and is apt to cake during mesh (F.M.) boric acid (77% through 100 mesh). The storage. varying amounts of water are added as a fine spray from Drying at temperatures below about 70 C. requires exa Water wash bottle. Six experiments are reported in the cessive drying time, and does not sufiiciently avoid caking. following table.

TABLE I Mixing Mixing Product without heat with heat wt., percent Water 100 added, Time, Temp, Time, Temp, M01 ratio, mesh, Exp. No. g. min. 0. min. C. Na O9 B203 NazOtBzOa percent 0 None 93 7. 09 54.3 0.147 47.6 20 20 26-22 23 22-95 5. 99 54.97 0.123 32.5 30 20 25-20 34 20-95 6.15 55.22 0.125 26.7 40 24 26. 5-20 24 20-104 5.26 55.61 0.106 27.9 51.6 20 25-12;.5 40 21-110 6.63 58.81 0.127 8.7 07 23 Room 20 20-70 7.91 56.10 0.159 2.1

At temperatures of about 115 C. or more the particles As compared to control Experiment 1, to which no may soften, and adhere to each other and to the walls of water is added, the amount of fines decreases on increasthe mixer. Temperatures between 90 and 105 C. have ing Water addition and is less than 30% through 100 been found to most consistently produce noncaking, dust mesh, Substantial improvement, at 3 Percent Water addif di h compositions, tion and is less than 10% through 100 mesh, a significant As heat is applied to the moist tumbling mixture the nnprovement at above about a 5 percent water addition. particles will roll over one another in light contact and amount of Water remammg be calculated by a the sodium pentaborate phase will associate itself with difference of the Nazo and B203 Welght percentages from 100 percent, the product generality containing about 30 the surfaces of single or multlple granules. As heating is percent to 40 Percent by Weight of Water X ray crYStaL continued, some of the water will be evaporated and any lographic examination of the product of Experiment 1 bOIaX dewhydfate which y have formed 15 eliminated shows it to contain H BO and borax 5 mol, whereas the from the product. Heat is discontinued when the granules i ti f h products f h succeeding -iare sufficiently distinct to remain as stable, noncaking, ments, in which water was added, shows that they connonpowdering mixtures of sodium borate. tain H BO borax 5 mol and sodium pentaborate.

3,531,278 5' 6 The effect of varying temperature, Water addition and tration of alternative starting materials are reported in mixing on the properties of the products, and the illusthe following table:

TABLE II Experiment No.

Borax 5 11101:

Type T.G. T.G. T.G. T.G. Amount, g 300 300 300 300 Boric acid:

T e RM. T.G. T G T G Amount, g 700 700 700 700 er: Amount, g O 20 30 4O Time of addition, min Mixing without heat:

Minutes None 20 20 24 Temp., C 26-22 25-20 26. -20 Mixing with heat:

Minutes 45 23 34 24 +25 31 +9 p, C r F g??? F 20-62 -1 r (1 t 1 i 7 i 5 7 Cakmg' days "i 140(15 e00(14) 600(14) 600) 600(14) F.F.(14) NaZO, wt. percent- 7. 09 5. 99 6. 15 5. 26 5. 61 6. 63 B203, Wt. percent- 54. 3 54. 97 55. 22 55. 61 56. 01 58. 81 M01 ratio, N azO/B 0. 147 0. 123 125 106 0. 113 0. 127

Experiment N o.

Borax 5 mol:

Type T.G. T.G. T.G. T.G- 12G. T.G. T.G. Amount, g 300 300 300 300 300 300 300 Boric acid:

Type F.M. RM. F.M. F.M. F.M. F.M. F.M. tAmount, g 700 700 700 700 700 700 700 a er:

Amount, g 60 71 71 70 70 80 100 Time of addition, min 7 3 34 3. 5 Mixing without heat:

nu es 35 21 118 17 1 Temp., 19. 7-20. 7 19. 5-21. 5 21-28 26. 1-19. 5 24-19. 4 22. 8-18. 4 23. 2-17. 8 Mixing with heat:

Minutes 21 33 Temp., C 19. 7-98 22-76 21-91 Caking, p.s.i., days- 0-F.F.(l7) F.F.(14) F.F.(14) NaQO, wt. percent. 6. 71 6. 56 B20 wt. percent-.. 55. 55 57. 20 M01 ratio, NHZO/BZOQ 0. 136 0. 129

Experiment No.

12 12a 13 13a 14 14a 15 Borax 5 mol:

yp g (0 Amount, g 300 537.1 537. 1 537. 1 Boric acid:

T e 1?.M. F M M Amount, g 700 462 9 462 9 462 9 Water.

Amount, g 100 51. 5 70 100 Time of addition, min Mixing without heat:

Minutes 22 20 19 Temp., C 17-21 20-26 20-28 20-30 Mixing with heat:

Minui es +21 37 +25 Temp., C 92-100 28-91 91-100 255-194 Caking, p.s.i., days- 0(25) F.I.(15) 0(25) F.F.(14) NazO, Wt. percent 12. 12. 28 12. 72 12. 49 B203, wt. percent 55. 30 56. 03 56. 82 55. 15 M01 ratio, Na O/B2O 0. 253 0. 246 0. 252 0. 255

Experiment No.

Borax 5 mol:

pe T.G. T.G. T.G. T.G. Amount, g 702. 5 702. 5 657 300 300 400 698 Borie acid:

T e- T.G. T.G. T.G. 'T.G. T.G. T.G. Amount, g 797. 4 797. 4 343 700 700 600 302 Water:

Amount, g 0 74 70 117. 9 50. 5 45 Time of addition, min Mixing without heat:

Minutes 1 31 32 80 4 15 18 57 Temp., C 23-28 22-59 20-25 Room 25-28 Room Mixing with heat:

Minutes 11 10 15 20 17 13 Temp., 28-90 32-90 20-113 20-102 28-90 20-112 Caking, p.s.i., days.-- (14) 0(14) F.F. F.F.(47) F.F.(27) F.F.(17) F.F.(24) Na2O1, Wt. pereent 13. 37 13. 12. 24 7. 06 7. 29 13. 76 15. 81 B203, Wt. percent. 60. 14 59. 34 57. 40 57. 57. 69 54. 77 53. 88 M01 ratio, Na2O/B O 0. 250 0. 258 0. 240 0. 137 0. 142 0. 282 0. 330

1 Type B. 1 AB dust was used instead of Borax 5 moi. 3 ABA dust was used instead of boric acid. 4 41 r.p.m.

The boric acid materials utilized in the experiments are granules of the fine mesh {F.M.) boric acid previously discussed, anhydrous boric acid granules (ABA) such as boric oxide and a technical granular (T.G.) grade of boric acid (40% through 100 mesh). The borax starting materials varied from the technical granular (T.G.) grade discussed above, a Type B grade (about 9% through 100 mesh) of borax 5 mol, and anhydrous borax (AB) dust. The AB analysis is 28.63% Na O and 64.76% B and the ABA product contains 92.8% B 0 with less than 0.1% Na O. In some of the experiments the mixer is covered during a portion of the heating step.

Caking tests are run by placing 140 ml. of the dry product in a standard spring-loaded sealed caking jar at approximately 4 p.s.i. The jar is placed in a cabinet which is cycled on a schedule of 12 hours at 75 F. and 12 hours at 115 F. for several days to two weeks. If not freefiowing (FF), the material was tested with a penetrometer with a A" head and the readings were multiplied by 4. A zero reading indicates the material is not free-flowing but is penetrated by the penetrometer head with a pressure so slight as not to record a reading. A product showing a p.s.i. value of about 150 or less has satisfactory fiow or caking properties.

Though 23% water addition significantly affects fines control (Table I) this amount of water produces a prodnot that unsatisfactorily cakes 600 p.s.i.) after 14 days. Products to which more than 3% by weight of water but less than 12% by weight of Water are added show quite satisfactory caking properties. Caking tendency, compared to the control experiment, at first decreases on the addition of water and then improves above 3% addition. In experiments in which the water is added instantaneously from a graduate or in which the dry mixture is heated to above 40 C. before water addition the mixture became a viscous, bal ed, unworkable mass.

Drying at temperatures below 70 C. gives unsatisfactory caking tendency which decreases at higher temperature. Consistently better results are apparent at temperatures from 90 C. to 105 C. It is necessary to add water at or near room temperature and to dry the prodnot at a high temperature. It can also be seen from a comparison of Experiments 7 and 8 of Table II that substantially increased agitation time causes a more caked product. The mixing interval without heat is usually around 20 minutes but can be as little as one minute (Exp. 4) or as much as 80 minutes (Exp. 20) without apparent effect on the caking results.

The mixing time with heat need not be unduly long. In Experiment 20 in which 11.79% Water is added, the moist mixture is only agitated with heat for 20 minutes.

A final experiment was conducted to explore the addition of the moist mixture to a preheated dryer with a view toward operation of the process in continuous production scale equipment.

Seventy-nine (79) grams of water was added in a fine stream to 300 g. T. G. Borax M01 and 700 g. T. G. boric acid in a mixer rotating at 41 r.p.m. and the moist mixture mixed twenty minutes without heat. The mixture Was removed from the mixer and the mixer was heated. The mixture was replaced and rapidly heated in five minutes to 100 C. and a non-caking, non-powdery product without undue lumping having the following screen analysis was obtained:

Nearly the same ratio product was found in the various sized particles except for the small percentage of lumps which were high in boric acid. This experiment demonstrates the feasibility of the hot drier technique, a procedure utilized in large scale production.

It should be understood that the foregoing disclosure relates only to preferred embodiments of the invention, and that numerous modifications or alterations are possible without departing from the spirit and scope of the invention as set forth in the following claims.

What is claimed is: 1. A method of preparing a sodium borate product having an Na O/B O molar ratio of from about 0.1 to 0.5 comprising the steps of:

adding 3 to 12 percent by Weight of water to a homogenous mixture of particles of anhydrous borax, borax pentahydrate, borax decahydrate or sodium pentaborate and particles of boric acid, boric oxide, metaboric acid or sodium pentaborate in sufficient amount to form sodium borate of said molar ratio while agitating the particles; heating the moist mixture with agitation at a tem.

perature of from about 70 C. to 115 C.; and

recovering a sodium borate composition of particles including sodium pentaborate having reduced fine content and caking tendency.

2. A method of forming a sodium borate composition having a mole ratio of Na O/B O of between about 0.1 and 0.35 comprising the steps of gradually adding 5 to 10% by weight of water to an agitated mixture of granules including a member selected from the group consisting of anhydrous borax, borax pentahydrate, borax decahydrate or sodium pentaborate with a member selected from the group consisting of boric acid, boric oxide, metaboric acid or sodium pentaborate, and heating the agitated mixture to a temperature of about C. to C.

3. A method of preparing a free flowing sodium borate product having a molar ratio of Na O/B O of 0.1 to 0.35, comprising the steps of:

mixing in the desired final ratio particles of borax pentahydrate with particles of boric acid; moistening said agitated particles with 5-10 percent by weight of water; and

heating the moistened mixture with agitation to a temperature of from 90 C. to 105 C.

4. A method according to claim 3 wherein the mixtue is agitated in a rotary mixer revolving at less than 60 r.p.m.

5. A method according to claim 3, in which the final product contains less than 30%100 mesh particles and from 30 percent to 40 percent by weight of water.

6. A method according to claim 5 in which the product contains less than 10%-100 mesh particles.

7. A method according to claim 5, in which the water is gradually added to the mixture of particles.

8. A method according to claim 5, in which 5 percent by weight of water is sprayed onto the agitated particles.

9. A process according to claim 8, in which the water is added at a temperature of from 15 C. to 40 C.

10. A process according to claim 3, in which the moist mixture is added to a mixer preheated to a temperature of from 70 C. to C.

11. A process according to claim 3 in which the product is classified and the 12 mesh particles are separated, crushed and returned to the product.

References Cited UNITED STATES PATENTS 2,643,947 6/1953 Connell.

2,662,810 12/ 1953 Taylor et a1.

2,998,310 8/1961 OBrien et al.

1,961,073 5/1934 Newman 2359 2,567,909 9/19'51 Linde 260623 (Other references on following page) 9 References Cited OBrien et a1. 71-128 Ball et a1. 23-59 Wright 71-109 Seibert 23-59 5 Galloway 167-42 Taylor et a1. 23-59 Schmitt 23-59 Mitchell et a1. 71-80 10 3,149,953 9/1964 Miller 71-93 3,274,052 9/1966 Yafie et a1. 167-42 LEWIS GOTTS, Primary Examiner G. HOLLRAH, Assistant Examiner US. Cl. X.R. 11-69; 252-1, 2

x ggg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 531,278 Dated September 29 1970 Inventor(s) Nelson P. Nies It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, line 12, after "r.p.m." delete Column 6, Table II, Experiment No. 21, in the line referring to Caking, psi, "F.F.(l7)" should be --F.F.(l6)--;

Column 8, line 55, "5" should be --3--.

bmaiu AN'D SEALED JAN 5 197' Atteat:

Mum," mm x. scam-m. m. Amomm Commissioner 0! Patents 

